CN107400903B - Three-dimensional nano porous copper modified foam nickel and preparation method and application thereof - Google Patents

Three-dimensional nano porous copper modified foam nickel and preparation method and application thereof Download PDF

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CN107400903B
CN107400903B CN201710469240.XA CN201710469240A CN107400903B CN 107400903 B CN107400903 B CN 107400903B CN 201710469240 A CN201710469240 A CN 201710469240A CN 107400903 B CN107400903 B CN 107400903B
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nickel
copper
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foamed nickel
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CN107400903A (en
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施志聪
程乙峰
柯曦
刘军
刘丽英
王乃光
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses a preparation method of three-dimensional nano porous copper modified foam nickel, which comprises the following specific steps: s1) self-assembling a polystyrene colloidal crystal template on a foamed nickel substrate; s2) electrochemically depositing copper on the surface of the foam nickel of the self-assembled polystyrene colloidal crystal template; s3) annealing the substrate after copper electroplating to remove the polystyrene colloidal crystal template. The invention obtains the three-dimensional nano-porous copper modified foam nickel by electrochemically depositing copper on the surface of the foam nickel of the self-assembled polystyrene colloidal crystal template and then removing the polystyrene colloidal crystal template at high temperature. The foam nickel has a large specific surface area and a three-dimensional through hole structure, and can reduce the effective current density of an electrode and inhibit the generation of lithium dendrites when being used as a current collector of a lithium secondary battery, and can contain deposited lithium metal, thereby effectively improving the coulombic efficiency and the cycling stability of the battery in the cycling process.

Description

Three-dimensional nano porous copper modified foam nickel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of porous metal composite materials, and particularly relates to three-dimensional nano porous copper modified foam nickel and a preparation method and application thereof.
Background
The foam metal material has high porosity, large specific surface area and unique three-dimensional network structure, and is widely applied to the fields of wave absorption, filtration, catalysis, energy storage and the like. The nickel foam has stable structure, good conductivity, corrosion resistance and low price, and is very suitable for being used as a carrier material. For example, the foamed nickel is often used as a current collector to support a battery electrode material, and the nano functional material supported on the surface of the foamed nickel can be used in the field of electrocatalysis. At present, the lithium battery has poor cycle performance and low safety performance due to the growth of lithium dendrites, and the copper foil in the current collector of the lithium battery is processed into a three-dimensional nano porous structure to inhibit the growth of the lithium dendrites so as to improve the performance of the battery, so that the method is an effective strategy for improving the performance of the lithium battery. The development of the preparation method of the nano-porous copper with simple process and low cost becomes a subject of great attention in the lithium battery industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of three-dimensional nano porous copper modified foam nickel. The method combines a template method and an electrochemical deposition method, constructs a three-dimensional nano porous copper structure on a foamed nickel substrate, creatively introduces the three-dimensional nano porous structure into a micron-sized porous structure, and forms a multi-stage foam composite structure.
The invention also aims to provide the three-dimensional nano-porous copper-modified foamed nickel prepared by the method. The three-dimensional nano porous copper modified foam nickel has a large specific surface area and a three-dimensional interconnected pore structure.
The invention further aims to provide application of the three-dimensional nano porous copper modified foamed nickel.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of three-dimensional nano-porous copper-modified foam nickel comprises the following specific steps:
s1, soaking foamed nickel into polystyrene emulsion, and taking out after evaporation drying treatment to obtain a foamed nickel substrate of the self-assembled polystyrene colloidal crystal;
s2, taking the foamed nickel substrate obtained in the step S1 as a working electrode, a platinum-plated titanium mesh as a counter electrode and a calomel electrode as a reference electrode, immersing the electrodes into plating solution, and performing electrochemical deposition in a three-electrode system to obtain a copper-deposited foamed nickel substrate;
and S3, annealing the foamed nickel substrate deposited with the copper obtained in the step S2, and removing the polystyrene colloidal crystal template to obtain the three-dimensional nano porous copper modified foamed nickel.
Preferably, in the step S1, the polystyrene emulsion is prepared by dissolving polystyrene in absolute ethyl alcohol, the mass concentration of the polystyrene emulsion is 25-45%, and the particle size of the polystyrene emulsion is 50-700 nm.
Preferably, the drying temperature in the step S1 is 50-80 ℃, and the drying time is 6-10 h.
Preferably, the plating solution in step S2 is CuSO4And H2SO4Mixed liquor of the said CuSO4The content of (A) is 0.06-0.2 mol/L, and the content of H is2SO4The content of (B) is 0.0005 to 0.002 mol/L.
Preferably, the current density of the electrochemical deposition in the step S2 is 9-15 mA cm-2The temperature of the electrochemical deposition is 20-40 ℃, and the time of the electrochemical deposition is 20-240 min.
Preferably, the temperature rise rate of the annealing in the step S3 is 0.5-5 ℃/min, the annealing temperature is 400-600 ℃, and the annealing time is 1-6 h.
The three-dimensional nano-porous copper modified foamed nickel is prepared by the method.
The three-dimensional nano porous copper modified foam nickel is applied to the field of lithium secondary batteries.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention combines a template method and an electrochemical deposition method to construct a three-dimensional nano porous copper structure on a foamed nickel substrate, and creatively introduces the three-dimensional nano porous structure into a micron-sized porous structure to form a multi-stage foam composite structure. Compared with the three-dimensional porous copper constructed on the planar conductive substrate, the three-dimensional nano porous copper constructed on the foamed nickel substrate has larger specific surface area, the three-dimensional porous copper pores are communicated, and the pore diameter and pore appearance are controllable.
2. The three-dimensional nano porous copper modified foam nickel has a large specific surface area and a three-dimensional through hole structure, and can reduce the effective current density of an electrode and inhibit the generation of lithium dendrites by using the foam nickel as a current collector of a lithium secondary battery, can contain deposited lithium metal, and effectively improves the coulombic efficiency and the cycling stability of the battery in the cycling process.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of nickel foam used in example 1 of the present invention.
Fig. 2 is a scanning electron microscope photograph of the three-dimensional nanoporous copper-modified nickel foam surface obtained in example 1.
Fig. 3 is a graph comparing coulombic efficiencies of 300 cycles of charge and discharge of the three-dimensional nanoporous copper-modified nickel foam of example 1 and the commercial nickel foam of comparative example 1 as a lithium negative electrode loaded on a current collector of a lithium battery.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Taking a polystyrene emulsion dispersed in absolute ethyl alcohol, wherein the particle size of polystyrene microspheres is 400nm, the mass ratio concentration of the emulsion is 45%, soaking foamed nickel into the polystyrene emulsion, putting the foamed nickel into an oven, and keeping the temperature at 60 ℃ for 6 hours to evaporate the emulsion. And taking out the foamed nickel after the evaporation is finished, thus obtaining the foamed nickel substrate of the self-assembled polystyrene colloidal crystal.
2. 180mL of basic plating solution (0.2mol/L CuSO) is taken4+0.0005mol/LH2SO4) Taking a platinum-plated titanium mesh as a counter electrode and a calomel electrode as a reference electrode, taking the sample prepared in the step 1 as a working electrode, and carrying out electrochemical deposition in a three-electrode system, wherein the working area of the electrode is 1cm2The deposition current is 12 mA; the deposition temperature is 30 ℃, the deposition time is 120min, the foamed nickel is taken out after the electrodeposition is finished, and the foamed nickel is repeatedly washed with deionized water for many times and dried with nitrogen.
3. And (3) annealing the sample prepared in the step (2) under the protection of 3% argon-hydrogen mixed atmosphere, wherein the heating rate is 0.5 ℃/min, the annealing temperature is 450 ℃, the annealing time is 4h, and after the annealing is finished, the sample is taken out, repeatedly cleaned by absolute ethyl alcohol, and dried by nitrogen gas, so that the three-dimensional nano porous copper modified foamed nickel can be obtained.
4. Taking the three-dimensional nano porous copper modified foamed nickel prepared in the step 3 as a cathode and a lithium sheet as an anode, and electrodepositing 1mAh ∙ cm on the three-dimensional nano porous copper modified foamed nickel-2The metal lithium of (1).
5. And (4) assembling the metal lithium electrode prepared in the step (4) and a lithium iron phosphate cathode into a full cell.
6. And (3) assembling the three-dimensional nano porous copper modified foamed nickel prepared in the step (3) and a lithium sheet serving as a counter electrode into a metal lithium half-cell.
7. And (3) performing charge-discharge cycle on the battery assembled in the step (6) for 5 weeks at a voltage range of 0-1V by using a current of 50 mu A so as to eliminate surface pollution and stabilize an SEI film. Then ∙ cm according to 1mAh-2The capacity density of (2) is 1mA ∙ cm-2The current density of (2) was subjected to charge-discharge cycles, and the charge cut-off voltage was 1V.
The nickel foam used in step 1 was characterized by scanning electron microscopy, and fig. 1 is a scanning electron microscopy picture of the surface of the nickel foam used in the example of the present invention. It can be seen from fig. 1 that the surface of the nickel foam is relatively smooth. And (3) characterizing the three-dimensional nanoporous copper-modified foamed nickel material obtained in the step (3) by using a scanning electron microscope, and fig. 2 is a scanning electron microscope photograph of the three-dimensional nanoporous copper-modified foamed nickel surface obtained in the embodiment. Wherein (a) is an amplification of 600 times, and (b) is an amplification of 4500 times. As can be seen from fig. 2, the three-dimensional nanoporous copper uniformly and densely coats the skeleton surface of the nickel foam. It can be seen from fig. 1 and 2(b) that the nickel foam grows a layer of nanoporous copper well. From FIG. 2(a), it can be seen that the nanoporous copper has a wormlike micropore morphology, uniform pore size, and interconnected pores.
Fig. 3 is a graph comparing coulombic efficiencies of 300 cycles of charge and discharge of the three-dimensional nanoporous copper-modified nickel foam of example 1 and the commercial nickel foam of comparative example 1 as a lithium negative electrode loaded on a current collector of a lithium battery. As can be seen from FIG. 3, the lithium metal is used as the negative electrode, the nickel foam and the three-dimensional nano-porous copper modified nickel foam are used as the counter electrodes respectively, the half-cell is assembled and the battery charge-discharge test is carried out, and the capacity density is1mAh∙cm-2The current density is 1mAh ∙ cm-2Under the test condition that the charge cut-off voltage is 1V, the three-dimensional nano porous copper modified foamed nickel has longer cycle life and higher cycle stability than the foamed copper, and has higher coulombic efficiency after 100 circles.
Example 2
1. Taking a polystyrene emulsion dispersed in absolute ethyl alcohol, wherein the particle size of polystyrene microspheres is 50nm, the mass ratio concentration of the emulsion is 30%, soaking foamed nickel into the polystyrene emulsion, putting the foamed nickel into an oven, and keeping the temperature at 50 ℃ for 10 hours to evaporate the emulsion. And taking out the foamed nickel after the evaporation is finished, thus obtaining the foamed nickel substrate of the self-assembled polystyrene colloidal crystal.
2. 180mL of basic plating solution (0.1mol/L CuSO) is taken4+0.002mol/L H2SO4) Taking a platinum-plated titanium mesh as a counter electrode and a calomel electrode as a reference electrode, taking the sample prepared in the step 1 as a working electrode, and carrying out electrochemical deposition in a three-electrode system, wherein the working area of the electrode is 1cm2The deposition current is 9 mA; the deposition temperature is 35 ℃, the deposition time is 200min, the foamed nickel is taken out after the electrodeposition is finished, and the foamed nickel is repeatedly washed by deionized water for many times and dried by nitrogen.
3. And (3) annealing the sample prepared in the step (2) under the protection of 3% argon-hydrogen mixed atmosphere, wherein the heating rate is 5 ℃/min, the annealing temperature is 450 ℃, the annealing time is 6h, and after the annealing is finished, the sample is taken out, repeatedly cleaned by absolute ethyl alcohol, and dried by nitrogen gas, so that the three-dimensional nano porous copper modified foamed nickel can be obtained.
4. Taking the three-dimensional nano porous copper modified foamed nickel prepared in the step 3 as a cathode and a lithium sheet as an anode, and electrodepositing 1mAh ∙ cm on the three-dimensional nano porous copper modified foamed nickel-2The metal lithium of (1).
5. And (4) assembling the metal lithium electrode prepared in the step (4) and a lithium iron phosphate cathode into a full cell.
6. And (3) assembling the three-dimensional nano porous copper modified foamed nickel prepared in the step (3) and a lithium sheet serving as a counter electrode into a metal lithium half-cell.
7. The battery assembled in the step 6 is subjected to charge-discharge cycle for 5 weeks at a current of 50 muA in a voltage range of 0-1VTo eliminate surface contamination and stabilize the SEI film. Then ∙ cm according to 1mAh-2Capacity density of 1mA ∙ cm-2The current density of (2) was subjected to charge-discharge cycles, and the charge cut-off voltage was 1V.
Example 3
1. Taking a polystyrene emulsion dispersed in absolute ethyl alcohol, wherein the particle size of polystyrene microspheres is 700nm, the mass ratio concentration of the emulsion is 25%, soaking foamed nickel into the polystyrene emulsion, putting the foamed nickel into an oven, and keeping the temperature at 75 ℃ for 5 hours to evaporate the emulsion. And taking out the foamed nickel after the evaporation is finished, thus obtaining the foamed nickel substrate of the self-assembled polystyrene colloidal crystal.
2. 180mL of basic plating solution (0.06mol/L CuSO) is taken4+0.001mol/LH2SO4) Taking a platinum-plated titanium mesh as a counter electrode and a calomel electrode as a reference electrode, taking the sample prepared in the step 1 as a working electrode, and carrying out electrochemical deposition in a three-electrode system, wherein the working area of the electrode is 1cm2The deposition current is 15 mA; the deposition temperature is 20 ℃, the deposition time is 20min, the foamed nickel is taken out after the electrodeposition is finished, and the foamed nickel is repeatedly washed by deionized water for many times and dried by nitrogen.
3. And (3) annealing the sample prepared in the step (2) under the protection of 3% argon-hydrogen mixed atmosphere, wherein the heating rate is 1 ℃/min, the annealing temperature is 600 ℃, the annealing time is 1h, and after the annealing is finished, the sample is taken out, repeatedly cleaned by absolute ethyl alcohol, and dried by nitrogen gas to obtain the three-dimensional nano porous copper modified foamed nickel.
4. Taking the three-dimensional nano porous copper modified foamed nickel prepared in the step 3 as a cathode and a lithium sheet as an anode, and electrodepositing 1mAh ∙ cm on the three-dimensional nano porous copper modified foamed nickel-2The metal lithium of (1).
5. And (4) assembling the metal lithium electrode prepared in the step (4) and a lithium iron phosphate cathode into a full cell.
6. And (3) assembling the three-dimensional nano porous copper modified foamed nickel prepared in the step (3) and a lithium sheet serving as a counter electrode into a metal lithium half-cell.
7. And (3) performing charge-discharge cycle on the battery assembled in the step (6) for 5 weeks at a voltage range of 0-1V by using a current of 50 mu A so as to eliminate surface pollution and stabilize an SEI film. Then ∙ cm according to 1mAh-2Capacity density of 1mA ∙ cm-2The current density of (2) was subjected to charge-discharge cycles, and the charge cut-off voltage was 1V.
Comparative example 1
1. Using commercial foam nickel as a cathode and a lithium sheet as an anode, and electrodepositing 1mAh ∙ cm on a nickel-copper current collector-2The metal lithium of (1).
2. And (3) assembling the metal lithium electrode prepared in the step (1) and a lithium iron phosphate negative electrode into a full cell.
3. And (3) assembling the foamed nickel prepared in the step (2) and a lithium sheet serving as a counter electrode into a metal lithium half-cell.
4. And (3) performing charge-discharge cycle on the battery assembled in the step (3) for 5 weeks at a voltage range of 0-1V by using a current of 50 mu A so as to eliminate surface pollution and stabilize an SEI film. Then ∙ cm according to 1mAh-2Capacity density of 1mA ∙ cm-2The current density of (2) was subjected to charge-discharge cycles, and the charge cut-off voltage was 1V.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A preparation method of three-dimensional nano-porous copper-modified foam nickel is characterized by comprising the following specific steps:
s1, soaking foamed nickel into polystyrene emulsion, and taking out after evaporation drying treatment to obtain a foamed nickel substrate of the self-assembled polystyrene colloidal crystal;
s2, taking the foamed nickel substrate obtained in the step S1 as a working electrode, a platinum-plated titanium mesh as a counter electrode and a calomel electrode as a reference electrode, and immersing the electrodes into a plating solution which is CuSO4And H2SO4Mixed liquor of the said CuSO4The content of (A) is 0.06-0.2 mol/L, and the content of H is2SO4The content of (B) is 0.0005 to 0.002 mol/L; carrying out electrochemical deposition in a three-electrode system to obtain a foam nickel substrate for depositing copper;
and S3, annealing the foamed nickel substrate deposited with the copper obtained in the step S2, wherein the annealing temperature rise rate is 0.5-5 ℃/min, the annealing temperature is 400-600 ℃, the annealing time is 1-6 h, and the polystyrene colloidal crystal template is removed to obtain the foamed nickel modified by the three-dimensional nano porous copper.
2. The method for preparing the three-dimensional nanoporous copper-modified nickel foam according to claim 1, wherein the polystyrene emulsion in step S1 is prepared by dissolving polystyrene in absolute ethanol, the mass concentration of the polystyrene emulsion is 25-45%, and the particle size of the polystyrene emulsion is 50-400 nm.
3. The method for preparing three-dimensional nanoporous copper-modified foamed nickel according to claim 1, wherein the drying temperature in step S1 is 50-80 ℃, and the drying time is 6-10 h.
4. The method for preparing three-dimensional nanoporous copper-modified nickel foam according to claim 1, wherein the electrochemically deposited nickel foam in step S2 has a current density of 9-15 mA cm-2The temperature of the electrochemical deposition is 20-40 ℃, and the time of the electrochemical deposition is 20-240 min.
5. A three-dimensional nanoporous copper-modified nickel foam, characterized in that it is prepared by the method according to any one of claims 1 to 4.
6. Use of the three-dimensional nanoporous copper modified nickel foam of claim 5 in the field of lithium secondary batteries.
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CN108538617A (en) * 2018-04-02 2018-09-14 中国科学院宁波材料技术与工程研究所 A kind of preparation method of three-dimensional ordered polyporous material
CN108878905B (en) * 2018-06-08 2020-05-22 浙江工业大学 Copper magnetic current collector, preparation process thereof and magnetic lithium air battery comprising copper magnetic current collector
CN109411764B (en) * 2018-10-30 2021-06-11 东南大学 Preparation method of nickel nitride-nickel foam composite lithium metal negative current collector
CN109817988A (en) * 2019-01-31 2019-05-28 山东金宝电子股份有限公司 A kind of preparation method of the lithium ion battery based on porous copper current collector
CN109772330B (en) * 2019-02-14 2021-11-05 安庆北化大科技园有限公司 Multilevel structure material with boron-doped cobalt hydroxide loaded on porous copper substrate and preparation method thereof
CN110615487A (en) * 2019-10-19 2019-12-27 石河子大学 CoNiO2Preparation method of nanoflower electrode material
CN112382764B (en) * 2020-11-12 2022-03-01 武汉理工大学 Lithium-philic copper-nickel double-metal-layer modified three-dimensional framework material and preparation method and application thereof
CN113881985B (en) * 2021-11-09 2024-03-22 重庆科技学院 Porous dendritic foam nickel, preparation method and application

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US5856047A (en) * 1997-01-31 1999-01-05 Ovonic Battery Company, Inc. High power nickel-metal hydride batteries and high power electrodes for use therein
CN103924260B (en) * 2014-04-14 2016-05-18 太原理工大学 Compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper and cobalt and preparation method thereof
CN105355925B (en) * 2015-10-30 2018-03-06 上海科技大学 A kind of preparation method of three-dimensional order nickel skeleton load germanium base lithium cell cathode material
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